Anthraquinone dyes



United States Patent 3,531,502 ANTHRAQUINONE DYES Gregoire Kalopissis, Paris, Jack Bertrand, Tremblay-les- 'Gonesses, and Andree Bugaut, born Ormancey, Boulogne-sur-Seine, France, assignors to Societe Anonyme dite: LOreal, Paris, France No Drawing. Filed Jan. 28, 1965, Ser. No. 428,867 Claims priority, appligcation France, Feb. 5, 1964,

Int. 01. e091) 1750; con 97/14 U.S. Cl. 260-380 5 Claims ABSTRACT OF THE DISCLOSURE The new compounds 1-hydroxy-2,4 bis-(p-dimethylaminophenyl)aminoanthraquinone and a quaternary salt of the compound of claim 1, which has the formula:

R1 CH3 in which R is a lower alkyl having 1-4 carbon atoms and A- is an anion; and hair dye compositions containing these compounds.

The process of reacting 1,3,4-trihydroxyanthraquinone with N,N-dimethyl-p-phenylenediamine to (p-dimethylaminophenyl)aminoanthraquinone.

O OH H H R1 GHa NH- 1l/ CH8 R1 cm in which R is a lower alkyl radical (for instance a methyl, ethyl, propyl or butyl radical); and A- is an anion, such as a halogen or a methylsulphate ion.

Examples of two compounds falling within the scope of the above-indicated Formula I are: bis-methyl-[lhydroxy 2,4 (p-trimethylammoniumphenyl)aminoanthraquinone]sulphate, that is the compound of Formula I where R is methyl and A" is methylsulphate, and [1- hydroxy-2,4 (p trimethyl-ammoniumphenyl) aminoanthraquinone] iodide, that is the compound of Formula I where R is methyl and A- is iodide.

The quaternary salts of this invention when applied to the hair give attractive grey shades of great intensity for which there is need in the art of hair-dyeing. They also have the advantage that they are very soluble in water over a very wide pH range, the aqueous solutions obtained being, in general, tolerant of all the practical conditions under which hair dyeing is carried out. Moreover, the quaternary salts when applied to hair have a 3,531 ,502 Patented Sept. 29, 1970 high resistance to sunlight, which is a most valuable property for hair dyes, and they also well withstand the presence of ingredients generally incorporated in dyeing compositions, such as hair penetrating and swelling agents, lustre-producing products and thickening agents.

1 hydroxy 2,4 (p-dimethylaminophenyl) aminoanthraquinone can be obtained by the reaction of N,N-dimethyl-p-phenylenediamine with purpurin, that is, 1,2,4- trihydroxyanthraquinone. The quaternary salts of l-hydroxy 2,4 (p dimethylaminophenyl)aminoanthra quinone can be obtained by reacting the latter compound with a quaternising agent such as methyl iodide or methyl sulphate.

The present invention also relates to a method of dyeing keratinic fibres, more particularly hair, by applying to the fibres a quaternary salt of this invention, allowing sufficient time to elapse for the said compound to exert its dyeing effect and then removing any unwanted excess of the compound from the hair. The quaternary salt is conveniently used in the form of an aqueous solution that is left in contact with the hair for about 15 to 60 minutes at ambient temperature, after which the hair is rinsed and washed.

The invention also comprises dyeing compositions suitable for dyeing keratinic fibres, which may take the form of solutions, emulsions, gels or creams, containing a quaternary salt of this invention. The dyeing composi tions preferably have a pH value of from 3 to 9.

The dye compositions of the" invention may be used in combination with other dyestufis which may or may not be quaternary salts of this invention or belong to the family of the anthraquinone dyestuffs.

The invention is illustrated by the following examples.

EXAMPLE I Preparation of 1-hydroxy-2,4-(p-dimethylaminophenyl) aminoanthraquinone There is heated for 8 hours at C. a mixture consisting of 264 g. of industrial purpurin, 64 g. of boric acid and 1018 g. of N,N-dimethyl(p-phenylenediamine), whereafter the mixture is diluted with 1.5 litres of alcohol and 3 litres of water. The crude product is thereafter separated and recrystallised from chlorobenzene. The product thus obtained has a melting point of 254- 255 C. and the following analysis.

Calculated (percent): C, 73.17; H, 5.69; N, 11.38.

Found'(percent): C, 73.65-73.37; H, 5.80-5.72; N.

EXAMPLE II Preparation of bis-methyl-[1-hydroXy-2,4-(p-trimethylammoniumphenyl)aminoanthraquinone] sulphate This compound is obtained by the action of 11.4 g. of methyl sulphate on a solution of 20 g. of l-hydroxy- 2,4-(p-dimethylaminophenyl)-aminoanthraquinone in 200 cc. of benzone. The quaternary ammonium obtained is separated, and it melts with decomposition at 200-203 C.

EXAMPLE III Preparation of [1 hydroxy-2,4- (p-trimethylammoniumphenyl)-aminoanthraquinone] iodide This compound is obtained by the action of methyl iodide (2.14 g.) on 1 hydroxy 2,4-(p-dimethylaminophenyl) aminoanthraquinone (3.32 g.). It decomposes at 260 C.

EXAMPLE IV A dyeing solution according to the invention is prepared by mixing:

Bis-methyl- 1 hydroxy-2,4- (p-trimethylammoniumphenyl)arninoanthraquinone] sulphateg. Sodium carbonate, q.s. for pH 7 Water, q.s. for 1000 cc.

This solution is applied to 100% white hair and left in contact therewith for 20 minutes at ambient temperature, whereafter the hair is washed, rinsed and dried.

The coloration thus obtained in the hair is violet-grey.

EXAMPLE V A dyeing solution according to the invention is prepared by mixing: 1-hydroXy-2,4- (p-trimethylammoniumphenyl) arninoanthraquinone] iodide-10 g. Sodium carbonate, q.s. for pH 7 Water, q.s. for 1000 cc.

This solution is applied to 100% white hair and left in contact therewith for 20 minutes at ambient temperature, whereafter the hair is rinsed, shampooed, rinsed again and dried.

The coloration thus obtained in the hair is blue-grey.

EXAMPLE VI A solution according to the invention is prepared by mixing:

Methyl- [4-hydroxyl B-methylmorpholinium) ethylaminoanthraquinone] sulphate 1.4 1- -dimethylaminopropyl -amino, 2-amino-4- nitrobenzene monohydrochloride 2.8 Bis-methy1- l-hydroxy-2,4- (p-trimethylammoniumphenyl) arninoanthraquinone] sulphate 8.5 Bis-methyl- 1,5 fl-methylmorpholinium) ethylaminoanthraquinone] sulphate 8.5

Sodium carbonate, q.s. for pH 8.5. Water, q.s. for 1000 cc.

When applied to light chestnut-coloured hair and left for minutes this mixture imparts a pearly-red tinge to the hair, after washing, rinsing and drying.

EXAMPLE VII A dyeing solution according to the invention is prepared by mixing:

N-monomethylnitro-p-phenylenediamine 6.5 l-(v-dimethylaminopropyl)-amino, 2-amino-4- nitrobenzene monohydrochloride 12 Bis-methy1[ 1-hydroxy-2,4- (p-trimethylammonium- 4 phenyl)arninoanthraquinone] sulphate 2 Bis-n1ethy1[ 1,4-(fl-methylmorpholinium) ethylaminoanthraquinone]sulphate 6 Sodium carbonate, q.s. for pH 8.5. Water, q.s. for 1000 cc.

in which R is a lower alkyl having 1-4 carbon atoms and A* is a halide or methyl sulfate.

3. The quaternary salt of claim 2, in which R is methyl.

4. Methy1-[1-hydroxy-2,4 bis (p trimethylammoniumphenyl -aminoanthraquinone] sulphate.

5. [1 hydroxy 2,4 bis (p trimethylammoniumphenyl) aminoanthraquinone] iodide.

References Cited UNITED STATES PATENTS 1,937,531 12/1933 Rogers et a1 260380 3,004,974 10/1961 Grossman et al. 260377 XR 3,192,117 6/1965 Kaiser et a1 167-88 3,368,942 2/1968 Kaiser et al. 167-88 OTHER REFERENCES Kalopississ et al., J. Soc. Cosmetic Chemists, Oxford, England: Pergamin Press Ltd., vol. 15, pages 411422 (1964).

LORRAINE A. WEINBERGER, Primary Examiner R. GERSTL, Assistant Examiner US. Cl. X.R. 810, 10.1, 39 

